CN1717826A - Metal alloy for electrochemical oxidation reactions and method of production thereof - Google Patents

Metal alloy for electrochemical oxidation reactions and method of production thereof Download PDF

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Publication number
CN1717826A
CN1717826A CNA2003801041742A CN200380104174A CN1717826A CN 1717826 A CN1717826 A CN 1717826A CN A2003801041742 A CNA2003801041742 A CN A2003801041742A CN 200380104174 A CN200380104174 A CN 200380104174A CN 1717826 A CN1717826 A CN 1717826A
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catalyst
complex
reduction
ruthenium
heat treatment
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CN100352090C (en
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曹立新
邹裕民
E·德卡斯特罗
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De Nora Elettrodi SpA
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De Nora Elettrodi SpA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention is relative to an alloyed catalyst for electro-oxidation reactions, and in particular to a binary platinum-ruthenium alloy suitable as the active component of a direct methanol fuel cell anode, as well as to the method of producing the same.

Description

The metal alloy and the manufacture method thereof that are used for electrochemical oxidation reactions
Background of invention
Direct methanol fuel cell (DMFC) is well-known thin film electrochemistry generator, and wherein oxidation takes place on anode methanol aqueous solution.Perhaps, for example the material (for example oxalic acid) of ethanol or other easy dry oxidation is as the anode feed of direct-type fuel cell for the light alcohols that can use other type, and catalyst of the present invention is suitable equally in these uncommon situations.
The low-temperature fuel cell of other type normally makes the hydroxide of pure state or form of mixtures in the anode chamber, compare with it, DMFC has great attraction, because DMFC uses liquid fuel, this can provide great advantage and charging easier and rapider aspect energy density.On the other hand, this Aalcohols fuel electroxidation is characterised in that its dynamics slowly, and in order to use under useful current density of reality and electromotive force, needs careful adjusted catalyst.DMFC has strong thermal limit, because their use amberplex as dielectric, and this element can not bear the temperature far above 100 ℃, and such temperature can influence methyl alcohol or other Aalcohols fuel oxidation kinetics largely negatively.
In in the past at least two ten years, there is the requirement of improvement anode catalyst all the time.The known best catalytic that is used for the light alcohols oxidation of these those skilled in the art is based on the binary or the triple combination of platinum and other noble metal.Especially, main preferred platinum-ruthenium bianry alloy aspect catalytic activity, and use their simultaneously as catalyst black (black) and for example supported catalyst on the active carbon, and they suitablely combine with amberplex in the situation of great majority and gas diffusion electrode structures combination.
Yet platinum and ruthenium be extremely difficult to be combined into real alloy: the disclosed Pt of prior art: Ru1: 1 typical combination almost always produces partially-alloyed mixture.The manufacture method typical case of the platinum of prior art and the binary combination of ruthenium is begun by the codeposition of colloidal particles on carbon carrier of the suitable compound of two kinds of metals, carries out electronation subsequently.After the chloride of platinum and ruthenium or the codeposition of sulphite, the electronation in water or the gaseous environment may rely on the very different reactivity of two kinds of metal precursors for reducing agent.The complex compound of platinum always can be reduced faster, occurs in to change to finish before being separated of two kinds of metals to be taken place.Therefore the alloy that can observe rich platinum usually and independent ruthenium are mutually.
Goal of the invention
An object of the present invention is to provide the method that obtains highly alloyed catalyst, this catalyst can be selected on the inert carrier and carry.
Another object of the present invention provides the method that obtains highly alloyed platinum-ruthenium combination, and this combination can show the high catalytic activity for methyl alcohol and other organic-fuel oxidation.
The electroxidation that another object of the present invention provides for organic substance has highly active catalyst.
Another purpose of the present invention provides the electrochemical process that can be used for lightweight organic molecule efficient oxidation.
Summary of the invention
On the one hand, the invention reside in the manufacture method of the catalyst of alloying, this method is begun by the complex compound of two kinds of metals and organic ligand, comprise decompose heat treatment and finish after reduction handle.On the other hand, the invention reside in the manufacture method of the platinum-ruthenium catalyst of alloying, this method is begun by the complex compound of two kinds of metals and organic ligand, comprise decompose heat treatment and finish after reduction handle.
Platinum-ruthenium catalyst that thermal decomposition when on the other hand, the invention reside in organic complex by two kinds of metals and reduction subsequently obtain.
Another aspect, the invention reside in methyl alcohol or other fuel electrochemical process in the oxidation of anode of fuel cell chamber, the catalyst of platinum-ruthenium alloyization that thermal decomposition when this fuel cell is equipped with by the organic complex of platinum and ruthenium metal and reduction subsequently obtain, and be to have the fuel cell of described catalyst.
DESCRIPTION OF THE PREFERRED
The reduction when method that is used to make the catalyst of alloying of the present invention can provide two kinds of metals, this can finish by careful selection precursor.In explanation subsequently, will still it will be apparent to those skilled in that this method has more generally validity for multiple other alloy with reference to the manufacturing of the high-alloying platinum-ruthenium binary catalyst that is used for fuel cell.
The unexpected discovery, different with the precursor of the salt of for example chloride or sulphite is, and the organic complex of platinum and ruthenium has closely similar decomposition temperature usually, and their difference is less than 20 ℃, and can hang down in some cases and reach 10 ℃.The latter is for example Pt and Ru and 2, the situation of the complex compound of 4-pentanedione (pentanedioate), and this part generally is also referred to as acetylacetonate (hereafter is " acac " commonly used in this area).Acetylacetonate is particularly preferred part, also can buy from the market and can directly handle because of it.
Implement preferable procedure of the present invention and must utilize the advantage of the close decomposition temperature of two kinds of precursors, change and reduce to the full extent simultaneously the formation of oxide when this can cause this complex compound.For this reason, the heat treatment that causes decomposing should begin with the heating steps of high heating rate, so that disassembling of ruthenium start give birth to before, the complex compound of platinum is not free basically to begin reaction, and should do not have air or other oxidizing substance in the presence of carry out whole heat treatment.
For fear of the too quick decomposition of platinum, must begin being not less than under 260 ℃ the temperature in any case preferably use catalyst reduction that hydrogen carries out to handle.Preferred platinum precursor is Pt (acac) 2It begins to decompose about 250 ℃, and preferred ruthenium precursor Ru (acac) 3Begin to decompose at 260 ℃.Therefore, preferably before reaching 260 ℃ temperature, do not have reducing agent to contact, and most preferred reduction temperature is about 300 ℃ with this catalyst material, for example 280 to 320 ℃.
Be the factor of considering that all these are different, in a preferred embodiment, inert atmosphere for example in the argon gas atmosphere complex compound to platinum and ruthenium carry out Fast Heating up to the final temperature that reaches 300 ± 20 ℃, wherein usually the complex compound of this platinum and ruthenium is adsorbed on inert carrier for example on the conductive carbon.In case reach final temperature, this reduction step can take place, for example by the hydrogen of 10-20% is sneaked into argon gas atmosphere up to finishing.In a preferred embodiment, reach after the final temperature, this catalyst material is remained in the inert atmosphere continue a few hours, for example 2 to 4 hours, as additional safety measure.After the transformation, close reducing agent stream, and in inert atmosphere with this catalyst cool to room temperature.The gas diffusion anode that uses in can the direct-type fuel cell with the catalyst that obtains like this and DMFC or other kind combines, and forms owing to have the alloy of higher degree, and this catalyst shows higher activity.
To utilize some embodiment that method of the present invention is illustrated now, and be not to mean method of the present invention is limited.
Embodiment 1
35g Vulcan XC-72 conductive carbon is suspended in 2 liters of beakers that contain 1 liter of acetone.Use Silverson RDispersal device acutely disperseed 5 minutes this mixture.In another boiling flask of 5 liters, with 21.9 gram Pt (acac) 2With 22.2 gram Ru (acac) 3Be suspended in 1.5 liters of acetone.Then, carbon dispersion is transferred to noble metal dispersion, stirs the gained mixture and by water-bath flask was maintained 25 ℃ simultaneously in 30 minutes.The slurry that obtains was carried out ultrasonic 30 minutes and the magnetic of spending the night stirs.Then by flask being placed 60 ℃ water-bath with acetone evaporated.After 6 hours, most of solvents all are removed.With nitrogen current by this mixture so that bring the evaporation to completion.Obtain the carbon that 79.0 grams have flooded catalysis material in this stage.
Speed with 30 ℃/minute in argon gas stream heats up to reaching 300 ℃ this sample.After thermally-stabilised, this straight argon air-flow was replaced to flow 200ml/ minute and contained the argon gas stream of 15% hydrogen.After 3 hours, this reducing atmosphere replaced with once more flow 100ml/ minute straight argon air-flow.After 3 hours, this reducing atmosphere replaced with once more flow 100ml/ minute straight argon air-flow.At last with this sample cool to room temperature.
Embodiment 2
Obtain being impregnated with Pt (acac) by the method among the embodiment 1 2And Ru (acac) 3VulcanXC-72 carbon sample.Speed with 30 ℃/minute in argon stream heats up to reaching 300 ℃ the gained sample, then, still in argon gas, temperature is remained on 300 ℃ and lasting 3 hours.At last, in argon gas, make the temperature cool to room temperature.In whole process Shen, do not use hydrogen.
Embodiment 3
Obtain being impregnated with Pt (acac) by the method in the previous embodiment 2And Ru (acac) 3Vulcan XC-72 carbon sample.At room temperature handle the gained sample, be heated to 300 ℃ with 30 ℃/minute speed then with 100ml/ minute and the argon gas stream that contains 15% hydrogen.After 300 ℃ keep 3 hours down, this air-flow is changed into pure argon and makes the sample cool to room temperature.
Embodiment 4
Obtain being impregnated with Pt (acac) by the method in the previous embodiment 2And Ru (acac) 3Vulcan XC-72 carbon sample.
By the method among the embodiment 1 this sample is heat-treated, just the heating rate of heating is 5 ℃/minute but not 30 ℃/minute.
Embodiment 5
Four kinds of catalyst that obtain in the previous embodiment are carried out X-ray diffraction.Estimating alloy by the displacement at 220 peaks forms.The particle size of the catalyst of embodiment 3 is more a lot of greatly than the particle size of other three kinds of catalyst.And, shown in the alloy phase in the following table is analyzed, in embodiment 1 and 2, almost form alloy (Ru=52-53% is with respect to theoretical value 50%) completely, yet under the condition of embodiment 4, alloying is (Ru=44%) not exclusively; Under the condition of embodiment 3, during from the beginning supply of hydrogen of thermal cycle, alloying level obviously insufficient (Ru=19.9%).
Show-pass through the alloy extent analysis that (220) peak is estimated
Sample # d(220) T(220) a-d(220) a-T(220) Mean value Ru(mol％)
1 1.3696 68.447 3.8738 3.8769 3.8753 52.5
2 1.3695 68.450 3.8735 3.8767 3.8751 52.8
3 1.3801 67.853 3.9035 3.9067 3.9051 19.9
4 1.3722 68.300 3.8812 3.8842 3.8827 44.5
Therefore this result is presented in the decomposition of two kinds of acetylacetonate complex compounds and should only uses argon gas.If before decomposing generation, used hydrogen, thereby can preferentially the platinum reduction be caused lower alloy extent, because Ru (acac) 3Reduction ratio Pt (acac) 2Slow a lot.As if on the contrary, decompose hydrogen treat influence in this respect afterwards fully can ignore.Simultaneously, the rate of heat addition should be relatively comparatively fast with guarantee basic simultaneously decomposition but not Pt (acac) 2(beginning about 250 ℃) follows by Ru (acac) 3The order of (beginning about 260 ℃) is decomposed.
(RDE) carries out the test of this catalyst by rotating disk electrode (r.d.e).By the 33mg supported catalyst is mixed rare ink of the catalyst for preparing the carbon carrying with 50ml acetone.It with total amount this ink of 10 microlitres is coated to the vitreous carbon rotation electrode of 6mm diameter with two to four coatings tip.
This electrode is placed the 0.5M H that contains 1M methyl alcohol under 50 ℃ 2SO 4In the solution.With platinum counterelectrode and Hg/Hg 2SO 4Reference electrode links to each other with the Gamry potentiostat with rotating disk electrode (r.d.e) (Perkin Elmer) with rotor (Pine Instrument).Under 2500RPM, carry out electric potential scanning (10mV/s) and write down the platform of representing the methanol oxidation that dissolves thus.Use the riser portions of this curve to assign to measure activity for methanol oxidation.The generation of this rising part is negative more, and this activity of such catalysts is big more.Carry out the comparison of reality by the baseline (electric current=0) that writes down this rotating circular disk volt-ampere curve with the intersection point of the curve rising part of different catalysts.With this value defined is ignition potential, and this activity that is worth low catalyst more is big more.In condition disclosed above, embodiment 1 and 2 catalyst all show-and 0.33V is (with respect to Hg/Hg 2SO 4) ignition potential, yet the Pt according to the carrying of the carbon of prior art: 1: 1 catalyst (De NoraNorth America of Ru, Inc., the commodity of E-TEK branch company) demonstrate-ignition potential of 0.18V, and be similarly the carbon carrying Pt catalyst of the prior art of U.S. De Nora North America commodity, show-ignition potential of 0.09V.
In the application's specification and claim, " comprising " and variant thereof are not the existence that intention is got rid of other element or supplementary element.
Can under the situation that does not deviate from the spirit and scope of the invention, realize the multiple modification of method of the present invention and catalyst, and should understand only to be intended that and limit the invention by the attached claim of stating.

Claims (23)

1. be used to make the method for the alloying catalyst that comprises multiple metal, this method comprises by heat treatment and reduction subsequently to be handled, and makes the precursor complexes while step of decomposition of described metal.
2. the process of claim 1 wherein the described precursor complexes that decomposes simultaneously is adsorbed on the inert carrier the optional conductive carbon that comprises of this carrier in advance.
3. the process of claim 1 wherein that the difference of decomposition temperature of described metal complex is less than 20 ℃.
4. the manufacture method that is used for the alloyed Pt-ruthenium catalyst of electroxidation, this method comprise by heat treatment and reduction subsequently to be handled, and makes platinum complex and ruthenium complex step of decomposition simultaneously, and wherein said platinum complex and ruthenium complex comprise organic ligand.
5. the method for claim 4 wherein is adsorbed on the inert carrier the optional conductive carbon that comprises of this carrier in advance with described platinum complex and the ruthenium complex that decomposes simultaneously.
6. the method for claim 4, the difference of the decomposition temperature of wherein said platinum complex and described ruthenium complex is less than 20 ℃.
7. the method for claim 4, the described organic ligand of wherein said platinum complex is identical with the described organic ligand of described ruthenium complex.
8. the method for claim 4, wherein said organic ligand comprises 2, the 4-pentanedione.
9. the method for claim 8, wherein said organic complex is Pt (acac) 2And Ru (acac) 3
10. the process of claim 1 wherein that described heat treatment carries out under inert atmosphere.
11. the method for claim 10, wherein said inert atmosphere comprises argon gas.
12. the process of claim 1 wherein that heating rate heating that described heat treatment comprises at least 20 ℃/minutes of uses is until at least 260 ℃ final temperature.
13. it is 280 to 320 ℃ that the method for claim 12, wherein said heating rate are at least 30 ℃/minute and described final temperature.
14. the method for claim 12, it is constant and lasting 2 to 4 hours wherein to keep described final temperature usually.
15. the process of claim 1 wherein that using hydrogen to carry out described reduction handles.
16. the method for claim 15, wherein said heat treatment is carried out under the argon gas inert atmosphere until the temperature that reaches 280 to 320 ℃, and carries out the described reduction under uniform temp usually and handle by sneak into 10 to 20% hydrogen in described argon gas atmosphere.
17. the process of claim 1 wherein that described reduction is the cooling processing that is cooled to room temperature under inert atmosphere after handling.
18. the method for claim 17, wherein said inert atmosphere comprises argon gas.
19. the catalyst that is used for the organic substance electroxidation that the method by claim 4 obtains.
20. electrochemical process, this electrochemical process comprise the oxidation of organic substance on the catalyst of claim 19.
21. the process of claim 20, wherein said organic substance comprises light alcohols.
22. the process of claim 21, this process are included in the anode chamber of fuel cell and make the methyl alcohol reduction.
23. in direct methanol fuel cell, comprise the improvement of the anode catalyst that uses claim 19.
CNB2003801041742A 2002-11-26 2003-11-25 Metal alloy for electrochemical oxidation reactions and method of production thereof Expired - Fee Related CN100352090C (en)

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US10/305,295 US20040101718A1 (en) 2002-11-26 2002-11-26 Metal alloy for electrochemical oxidation reactions and method of production thereof

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AU2003283426A1 (en) 2004-06-18
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ATE392721T1 (en) 2008-05-15
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